Process for improving vegetable textile material



Patented Apr. 14, 1931 PATENT OFFICE LEON LILIENIELD, OF VIENNA, AUSTRIA PROCESS FOR IMPBQVING VEGETABLE TEXTILE MATERIAL No Drawing. application filed llay 19, 1925, Serial No. 31,446, and in Austria Il jay 30, 1924.

This invention relates to a process for improving textile materials of vegetable origin. According to the invention very valuable properties are conferred upon woven and spun material of vegetable origin by treating them in presence of alkalies with an inorganic ester of a monohydric alcohol, for

instance a dialkyl-sulplrate, an alkyl halide or an aralkyl halide. This process imparts to the materials a silky gloss of great brilliance and a pleasing finish of elastic feel.

' The invention consists in treating with an inorganic ester of a mono-hydric alcohol, for V instance, a dialkyl sulphate, an alkyl halide or an aralkyl halide, in presence of alkali, I spun or woven material consisting of or containing a vegetable fibre, particularly cotton.

The material may be treated with the inorganic ester and.the alkali either simultaneously or in either sequence.

Among the alkalies which can be used, the most important are the caustic alkalies. Alkali metal sulphides may, however,'be used, although the results obtained are usually less satisfactory.

There may be treated according to the invention all vegetable fibres, such as linen, flax, hemp, ramie, jute, and especially cotton, in the form of pure vegetable (for example, pure 0 cotton) or mixed goods, in the form of yarn in skeins or cops, or in the form of warps.

The textile goods consisting of or containing the vegetable fibre may be treated ac- 3 cording to the invention either in the crude 5 state or after a preliminary treatment (for instance, boiling, or heating under pressure with sodium carbonate solution or dilute alkali solution or both), either moistened or unmoistened, with or 'without removing the -fatty constituents, either unbleached or after bleaching with an oxidizing or reducing bleaching agent, and with or without mer-' cerizing. The material may also be previously prepared in known manner by treatment with a hydrolyzing or gelatinizing agent (for example with a strong mineral acid such as sulphuric acid of 49-60 Baum specific gravity, phosphoric acid of -57v Baum specific gravity. hydrochloric acid of 24 Baum specific gravity, or nitric acid of 43-46" Baum specific gravity, or more, with an ammoniacal solution of cupric oxide, or with a cold or hot solution of calcium thiocyanate or other thiocyanate). The preliminary treatment may also consist in a combination of two or more of these processes.

The conditions under which the process is carriedout according to the invention may vary within Wide limits, and the invention is not limited to the illustrative examples of its practical application, which follow.

As examples, the following methods of carrying out the invention are given.

The first method consists in treating the woven or spun material first with a solution of an alkali and then acting on it with an inorganic ester of a monohydric alcohol, such as a dialkyl sulphate, an alkyl halide or an aralkyl halide. The textile material may be treated with the alkali solution in various ways; for example by dipping or soaking it in a small or large excess of the alkali solution; by dipping or soaking it in the alkali solution and removing the excess of alkali solution by squeezing, centrifuging or the like; by impregnating it in an impregnating mill, pgger or the like; by padding it between smooth or engraved rollers in a padding machine; by coating by means of closely engraved rollers in a rouleaux machine, advantageously with the addition of a thickening agent; by spraying, or by any other known method.

As alkali solution there may be used, for example, a solution of caustic soda oi: 10-50 per cent. strength; a solution of caustic soda of 12-40 er cent. strength has been found very suita le.

The quantity of alkali solution with wh ch the material is to be impregnated, or whlch is to be retained by the material, may be varied within wide limits. Thus, for instance, satisfactory results have been obtained when this quantity is from 2 to 10 times the weight of the textile material. As a rule, a quantity of from 2 to 4 times the weight of the material will be found to be suflicient.

The temperature of the alkali solution may also be chosen from a very wide range. Useful results are obtained at temperatures of strength .of the alkali solution.

from C. to +50 C. according to the Generally, if the alkali solution is not too weak, the process may be conducted at room temperature.

In order that the alkali solution may penetrate the fibres thoroughly, and increase the lustre, the woven or spun material may be caused topass between rollers during the treatment with the alkali solution, or it may otherwise be subjected to a high pressure. If desired the alkali solution may contain some alcohol.

The textile material which has been treated with alkali is then treated with an inorganic ester of a monohydric alcohol, for example with a dialkyl sulphate or an alkyl halide or an aralkyl halide, either immediately after the alkali treatment, or after standing (ripening? at room temperature or above for a short or ong period, and either in the wet state or after it has previously been partly or completely dried. The ester may be brought into contact with the material which has been treated with the alkali solution either as such, or dissolved in a suitable solvent, or suspended in an indifferent medium. There may be used as a solvent benzene, alcohol, a mixture of benzene and alcohol, or any other solvent. In order that the ester may be uniformly distributed throu bout the textile material, it

may be used, i desired, in admixture with a suitable binding or thickening agent, such as starch, dextrin, British gum, albumen or the like.

The ester may be added in various ways to the material which has been treated with the solution of alkali. The material may be impregnated or coated on one or both sides with the ester, or with a solution or emulsion thereof (in which case any excess may be removed, 1f deslred, by presslng or centrlfuging), or

the ester or a solution or suspension thereof may be rolled into the material. Any other method may, however, be employed, such as spraying. In order that the distribution of the ester throughout the textile material may be as uniform as possible, the material may, if desired, be passed through one or more pairs of rollers during the treatment, or may be subjected to pressure by other means.

For.introduci ng the ester there may be used any suitable apparatus known in the art of finishing or printing textiles.

The material which has been treated with the inorganic ester is then washed either directly, or soon after addition of the ester, or after it has been in contact with it for a short or long period (for example 2i hours) at room temperature or at a higher temperature (for example 50100 Q), and if deslred after previously having been dried, or it may advantageously be treated with a cold or warm solution of an inorganic or an organic acid, or of an acid salt, or of an f ammonium or other salt, or with a tannin ing operation.

solution or a formaldehyde solution, or with any other precipitating agent known in the viscose or ammoniacal-copper-oxide-cellulose industries, or with a mixture of such precipi tatin agents, and then washed and dried. It may e steamed before or after washing. 1

Any of the subsidiary operations usual in mercerization or proposed for this purpose may also be used in the present invention, for examplelustering, pressure, mechanical beating, and the like.

In order to produce a hi h grade, silky lustre, it is essential that the textile fibre should be stretched. It may be stretched throughout all the operations, that is, from,

the impregnation with the alkali solution at the commencement, to the washing and dry- The material may also be stretched only during the action of the alkali solution or of the inorganic ester, or it may be stretched after the impregnation with the alkali solution, and may remain stretched during the actionof the ester, during the.

treatment with the acid, salt, or the like, and

during the washing and optionally during The second method of carrying out the invention consists in reversing the order of the operations of the first method; that is to say, the textile material is first treated with the inorganic ester as such, or with a solution or a suspension thereof, and is then introduced into the alkali solution or impregnated, coated, or sprinkled, or sprayed therewith.

Since the inorganic esters have noaction on the fibre in absence of alkali, the treatment with alkali solution may follow the treatment with the inorganic ester at leisure. After the material has been brought into contact with the alkali solution, the inorganic ester is allowed to act for a certain time; this action may proceed at room temperature or at a higher temperature. In respect of the other conditions such as the quantitative proportions. the temperatures, the duration of the reaction, the stretching, and the finishing of the material, the conditions given in the first method of carrying out the process are equally applicable.

. By an appropriate selection of the work-' ing conditions. there may be obtained by the presentinvention silk-like effects which are ar superior to those which can be obtained by the usual methods of. memorization. In

lit

addition to the silky lustre, the woven or spun material possesses a finish which has a valuable, elastic feel. The silky lustre may be improved by one or more repetitions of the process.

The process according to the invention is also suitable for producing patterns, for which the following methods are of consequence:

1. Before the treatment with alkali solution, a pattern is printed or stencilled on the material by means of a reserve paste which prevents either mechanically or chemically the absorption of the alkali solution. Materials suitable for the reserve are, for instance, albumen, gums, acids (such as acetic acid, citric acid, tartaric acid, or an inorganic acid), alum, aluminium sulphate, ammonium sulphate, or other salts. The material is then treated with alkali solution and an inorganic ester of a monohydric alcohol, advantageously with a dialkyl sulphate, an alkyl halide or an aralkyl halide according to the method described. in illustration of the first method of carrying out the invention. This modification of the process permitsthe production of a lustrous pattern upon a dull background or vice versa.

2. The alkali solution, mixed with a suitable thickening agent (such as starch, denatured albumen, a cellulose-hydrate which is soluble in alkali, an alkylor oxyalkyl-cellulose derivative which is soluble in alkai or in water, or a cellulose-hydroxyparaflinmonocarboxylic acid or the like), is printed in any desired pattern on the woven material, which is then treated with an inorganic ester of a monohydric alcohol, advantageously with a dialkyl sulphate, an alkyl halide or an aralkyl halide as already described. The.

ell'ects obtained resemble those obtained according to l.

3. After treatment with alkali solution and if necessary after drying, the material is printed with a reserve which prevents, either mechanically or chemically, the reaction between the alkali-cellulose and the inorganic ester. There may be used for this purpose,

acid, albumen, kaolin, zinc-fi white, or the like. There may also be added for example, an

to the reserve paste a dyestuif or pigment. After printing with the reserve the material is treated with the inorganic ester as in the first method of carrying out the invention, and is then treated with an acid or salt, and dried. This method yields strongly lustrous efl'ects on a less lustrous background, or vice versa.

4. Pattern effects may also be produced by impregnating the woven material with alkali solution according to the first method of can rying out the invention, then, if necessary,

after previously drying the material, printing it with an inorganic ester of a monohydric alcohol, advantageously with a dialkvl sulphate, an alkyl halide, or an aralkyl halide, dissolved or suspended in a suitable thickening medium (for example British gum, starch or dextrin) with or without the addition of a dyestufi', and then finishing the material according to the first method of carrying out the invention. Highly lustrous effects on a less lustrous background may thus be obtained.

5. An inorganic ester of a monohydric alcohol, advantageously a dialkyl sulphate, an alkyl halide or an aralkyl halide, in the form of a solution or suspension, is printed on the woven material with the aid of a thickening agent, and the material is then subjected, with or without drying, to the action of alkali solution. The effects are similar to those obtained in 3 and 4.

The following examples illustrate the invention, the parts being by weight 1. (a) Bleached or unbleached cotton fabric or yarn is treated with caustic soda solution of 25-40 per cent. strength for a period of from 5 minutes to 12 hours at room temperature, and the excess of the solution removed by wringing or centrifuging, until the material retains about 2 -3 times its weight or any other desired proportion, of the solution. The impregnated material is then treated either immediately or after it has been allowed to stand for 3-72 hours, with dimethyLSulphate, diethyl-sulphate, ethyl iodide, methyl iodide, ethyl bromide or benzyl chloride, either alone, or in the form of a solution bf -50 per cent. strength in benzol or chloroform or carbon tetrachloride or in alcohol or the like, or in the form of a suspension of 10-50 per cent. strength in a solution of British gum of -25 per cent. strength. The yarn or fabric may be impregnated or coated on one or both sides with the ester, or the solution or suspension thereof, or the ester, or the solution or suspension thereof may be rolled on to or into the textile material. There is practically no limit to the quantity of the ester which may be incorporated with the yarn or fabric which has been impregnated with caustic soda solution. For reasons of economy, however, it is advisable'to use a quantity equal to not more than to 1 times the Weight of the cotton goods, particularly as excellent effects may be obtained with this amount or even with a smaller amount. After the material has been in contact with the inorganic ester for a short period (for example 10 minutes), or for a longer period (for example 12 hours), it is washed and dried or introduced into a dilute solution (for example of 10-20 per cent. strength) of sulphuric or acetic acid, or into a solution ofammonium chloride or ammonium sulphate of 20-30-per cent.

as 5 minutes), or for a longer period (such as several-hours), and is then washed and dried. The fixing material may be applied to the fabric by sprinkling, spraying or the like.

During the foregoing operations, the fabric or yarn should be stretched for at least a part of the time, for instance, during the action of the alkali solution. If the duration of-the action of the alkali solution and of the ester is not too long, the material may be in the stretched condition throughout all the operations. It may,- however, be sretched after it has been impregnated with the alkali solution, and remain stretched during the whole or a portion of the treatment with the ester, and if necessary during the treatment with the acid or salt. The textile material may also be stretched during the washing operation, though this is ad-v vantageous only in respect of the silk-like lustre.

According to the process described in this example, there is obtgnbd a high-grade, silk-like lustre, and a pleasing finish o elastic feel.

(6) The procedure is as'in a, with the exception that the action of the inorganic ester is carried out at raised temperature. For this purpose, the material which has been impregnated with caustic soda solution and brought into contact with the ester is maintained for 10 minutes to 1 hour at a temperature .of 50-100 (1., for instance at 80 C.

(a) The procedure is as in a or b, with the exception that the caustic soda solution used is of 18-20. per cent. strength instead of -40 per cent. strength. The final product has a very beautiful silky lustre.

2. Bleached or unbleached cotton fabric or yarn is impregnated with a solution of 10 per cent. strength of di-methyl sulphate, di-ethyl sulphate, ethyl iodide, methyl iodide or ethyl bromide in alcohol or benzol The material impregnated sired, after removal of the excess by squeezingor centrifugin into a solution of caustic soda solution of allowed to remain in contact with the solution for a period of from 10 minutes to 2 hours and then finished as described in Example .1 (a). The fabric may be stretched ples 1 (a) to 1 (c), with the exceptionthat' during or after the treatment with the al- ;kali solution. A silky lustre is produced.

3. The procedure is as in any of Examinstead of aqueous caustic soda solution of 30-40 per cent. strength,

4. The procedure is exactly as in any of the preceding examples, with the exceptlon that the material is treated with strong sulphuric acid before being treated according to the invention. When sulphuric acid of 49-50 Baum specific gravity is used, the treatment with the acid may occur at room temperature'for a period of from several seconds to several minutes, or even longer.

.When a stronger acid is used, for example,

of 52-54 Baum specific gravity, the treatment may occupy only several seconds at room temperature, but a longer period if the acid be cooled to 0 C. or below.

The treatment with sulphuric acid may also precede mercerization of the fabric, for

example, with caustic soda solution of 10.

per cent. strength at a low temperature or with a stronger caustic soda solution, for

instance, one of 18 10 per cent. strength at The expression textile material in the .description and claims means, where the context permits, all vegetable fibres such as,

flax, linen, hemp, ramle, jute and articularly cotton, and the like, in the orm of fabric of the pure vegetable product (such as pure cotton fabric) or mixed fabric, or yarn which, if desired, may be in the form of skeins, cops or warps.

The expression precipitating agent means acids, salts, acid salts, m xtures of acids and salts, in short all precipitatin agents known in the viscose industry as we as organic acids or aqueous solutions there of, alcohols, tannic acids, and. formaldehyde.

I claim: I v I 1. A process for improving vegetable textile material which comprises treating it with an inorganic ester of a monohydric alcohol in the presence of alkali. 2. A process for improving vegetable tex tile material which comprises treating it with an alkali solution, and thereafter reactin on .120

it with an inorganic ester of a monohy ric alcohol.

3. A process for improving vegetable textile material which comprises treating it with an alkali solution and thereafter acting on it with an inorganic ester of a monohydric alcohol in presence of at least a portion of the alkali solution used in the treatment.

4. A process for improving vegetable textile material, which comprlses treating it with an alkali solution, and thereafter acting llti tlti

till

on it with an inorganic ester of a monohydric alcohol in presence of the alkali solution remaining in the material.

5. A process for improving vegetable textile material, which comprises treating it with an alkali solution and after removing at least a portion of the water by drying, reacting on it with an inorganic ester of a monohydric alcohol.

6. A process for improving vegetable textile material, which comprises treating it' with an alkali solution, andthereafter'reacting on at least one side with an inorganic ester of a monohydric alcohol.

7. A process for improving vegetable textile material, which comprises treating it with a solution of an alkali and thereafter reacting on at least one side with an inorganic ester of a monohydric alcohol mixed with a thickening agent.

8. A process for improving vegetable textile material, which comprises treating it with an alkali solution and reacting on it at certain parts with an inorganic ester of a monohydric alcohol.

9. A process for improving vegetable textile material, which comprises treating it with a solution of an alkali and printing it in the presence of alkali with an inorganic ester of a monohydric alcohol mixed with a thickening agent.

10. A process for improving vegetable textile material, which comprises treating it at certain parts with an alkali solution and thereafter reacting on it with an inorganic ester of a monohydric alcohol.

11. The process for improving vegetable textile material which comprises treating it with an inorganic ester of a monohydric alcohol at least at certain parts in the presence of a solution containing alkali metal hydroxide.

12. A process for improving vegetable textile material, which comprises acting on it at a raised temperature, in the presence of an alkali, with an inorganic ester of a monohydric alcohol.

13. A process for improving vegetable textile material, which comprises treating it with an alkali solution and thereafter reacting on it at a raised temperature with an inorganic ester of a monohydric alcohol.

let. A process for improving vegetable textile material, which comprises acting on it in presence of an alkali with an inorganic ester of a monohydric alcohol, thereafter treating it with a precipitating agent and washing it.

15. A process for improving vegetable textile material, which comprises treating it with an alkali solution, thereafter reacting on it with an inorganic ester of a monoliydric alcohol, and thereafter treating it with a precipitating agent and washing it.

it. A process for improving vegetable textile material, which comprises acting on it in'presence of an alkali with an inorganic ester of a monohydric alcohol and stretching the material during at least a portion of the process.

17. A process for improvingvegetable textile material, which comprises treating it with an alkali solution, thereafter reacting on it with an inorganic ester of a monohydric alcohol, and stretching the material during at least a portion of the process.

18. A process for improving vegetable textile material, which comprises treating it with an alkali solui-ion, thereafter reacting on it with an inorganic ester of a monohydric alcohol, thereafter treating it with a precipitating agent, and washing it, and stretching the material during at least a portion of the process.

19. A process for improving vegetable textile material, which comprises treating it with a dialkyl sulphatein presence of alkali.

20. A process for improving vegetable textile material, which comprises treating it with an alkali solution, and thereafter reacting on it with a dialkyl sulphate.

. 21. A process for improving vegetable textile material, which comprises treating it with an alkali solution and thereafter acting on it with a dialkyl sulphate in presence of at least a portion of the alkali solution used in the treatment.

22. A process for improving vegetable textile material, which comprises treating it with an alkali solution, and thereafter acting on it with a dialkyl sulphate in presence of the alkali solution remaining in the material.

23. A process for improving vegetable textile material, which comprises treating it with an alkali solution and after removing at least a portion of the water by drying, reacting on it with a dialkyl sulphate.

24:. A process for improving vegetable textile material, which comprises treating it with an alkali solution and thereafter reacting on it with a dialkyl sulphate in presence of a thickening agent.

25. A process for improving vegetable. textile material, which comprises treating it with an alkali solution and thereafter reacting on at least one side with a dialkyl sulphate.

26. A process for improving vegetable textile material, which comprises treating it with a solution of an alkali and thereafter reacting it on at least one side with a dialkyl sulphate mixed with a thickening agent.

27. A process for improving vegetable textile material, which comprises treating it with an alkali solution and reacting on it at certain parts with a dialkyl sulphate.

28. A process for improving vegetable textile. material, which comprises treating it I with a solution of an alkali and printing it Bil 4 an alkali solution, thereafter reacting in the presence of with a dialkyl sulphate mixed with a thickening agent.

29. A process for improving vegetable textile material, which comprises treating it at certain parts with an alkali solution and thereafter reacting on it with a dialkyl sulphate.

30. A process for improving vegetable tex- I tile material, which comprises treating it an alkali with a dialkyl sulphate.

32. A process for improving vegetable textile material, which comprises treating it with an alkali solution and thereafter reactinon it at a raised temperature with a dia kyl sulphate.

33. A process for improving vegetable textile material, which comprises acting on it in presence of an alkali with a dialkyl sulphate, thereafter treating it with a precipitating agent and washing it.

34. A process for improving vegetable tex tile material, which comprises treating it with an alkali solution, thereafter reacting on it with a dialkyl sulphate, thereafter treating it with. a precipitating agent and washing it.

35. A process for improving vegetable textile material, which comprises acting on it in presence of an alkali with a dialkyl sulphate and stretching the material during at least a portion of. the process.

36. A process for improving vegetable textile material, which comprises treating it with an alkali solution, thereafter reacting on it with a dialkyl sul hate, and stretching the material during at east a portion of the process.

37. A process for improving vegetable textile material, which comprises treating it with on it with a d-ialkyl sulphate, then treating it with a precipitating agent, and washing it, and stretching the material during at least a portion of the process.

38. As new products, silk-like lustrous vegetable textile materials, which contain a derivative of cellulose in which a portion of the hydrogen of the cellulose has been exchanged for the residue of a monohydric alv cohol.

39. As new products, silk-like lustrous, ve etable textile materials which contain an a l derivative of cellulose.

40. As new products, silk-like lustrous, vegetable textile materials which contain an aralkyl derivative of cellulose.

41. The process of treating vegetable tex- I 

